Frankel E N, Neff W E, Rohwedder W K, Khambay B P, Garwood R F, Weedon B C
Lipids. 1977 Nov;12(11):901-7. doi: 10.1007/BF02533309.
A structural investigation of autoxidation products of methyl oleate was carried out by gas chromatography-mass spectrometry (GC-MS) of trimethylsilyl (TMS) ether derivatives. GC-MS using computer plots of selected masses afforded structural assignments of GC peaks due to incompletely resolved mixtures. This method provided evidence of epoxy and keto esters which are not completely separated from the main components consisting of the TMS derivatives of the allylic hydroxy esters. Use of an MS-computer system also showed that the hydroxyoctadecanoate TMS ethers were partially separated by GC. The use of synthetic hydroxyoctadecanoates for the first time enabled us to demonstrate the quantitative reliability of a GC-MS computer summation approach to analyze the isomeric composition of oleate hydroperoxides (as the saturated TMS ether derivatives). Consistently higher concentrations were found of the 8- and 11-hydroperoxides than of the 9- and 10-hydroperoxides. Minor products of autoxidation identified by GC-MS include allylic enones, isomeric epoxyoctadecanoates, dihydroxyoctadecenoates, and dihydroxyoctadecanoates.
通过对三甲基硅烷基（TMS）醚衍生物进行气相色谱 - 质谱联用（GC - MS），对油酸甲酯的自氧化产物进行了结构研究。由于混合物未完全分离，利用选定质量的计算机图谱的GC - MS对GC峰进行了结构归属。该方法提供了环氧酯和酮酯的证据，它们与由烯丙基羟基酯的TMS衍生物组成的主要成分未完全分离。使用MS - 计算机系统还表明，羟基十八烷酸酯TMS醚通过GC部分分离。首次使用合成羟基十八烷酸酯使我们能够证明GC - MS计算机求和方法用于分析油酸氢过氧化物（作为饱和TMS醚衍生物）的异构体组成的定量可靠性。一致发现8 - 和11 - 氢过氧化物的浓度高于9 - 和10 - 氢过氧化物。通过GC - MS鉴定的自氧化次要产物包括烯丙基烯酮、异构环氧十八烷酸酯、二羟基十八碳烯酸酯和二羟基十八烷酸酯。
